Fungicide mixtures based on pyride amides and morpholine derivatives or piperidine derivatives

ABSTRACT

Fungicidal mixtures comprising as active components 
     a) an amide compound of the formula I 
     
       
         A—CO—NR 1 R 2   I 
       
     
      in which 
     A is an aryl group or an aromatic or non-aromatic, 5- or 6-membered heterocycle which has from 1 to 3 hetero atoms selected from O, N and S; 
     where the aryl group or the heterocycle may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, halogen, CHF 2 , CF 3 , alkoxy, haloalkoxy, alkylthio, alkylsulfynyl and alkylsulfonyl; 
     R 1  is a hydrogen atom; 
     R 2  is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3 substituents which are selected, independently of one another, from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cyclo-alkenyloxy, phenyl and halogen, where the aliphatic and cycloaliphatic radicals may be partially or fully halogenated and/or the cycloaliphatic radicals may be substituted by from 1 to 3 alkyl groups and where the phenyl group may have from 1 to 5 halogen atoms and/or from 1 to 3 substituents which are selected, independently of one another, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and where the amidic phenyl group may or may not be condensed with a saturated 5-membered ring which may or may not be substituted by one or more alkyl groups and/or may have a hetero atom selected from O and S, and 
     b) a morpholine or piperidine derivative II selected from the group of the compounds IIa, IIb, IIc, IId [sic] and IIe [sic]                    
     in a synergistically effective amount.

This application is a 371 of PCT/EP98/08229 filed Dec. 15, 1998, whichclaims priority for German Patent 19756406.2 filed Dec. 13, 1997.

The present invention relates to fungicidal mixtures for controllingharmful fungi and also to methods for controlling harmful fungi usingsuch mixtures.

WO 97/08952 describes mixtures of amide compounds of the formula I

A—CO—NR¹R²  (I)

in which

A is an aryl group or an aromatic or non-aromatic, 5- or 6-memberedheterocycle which has from 1 to 3 hetero atoms selected from O, N and S;

where the aryl group or the heterocycle may or may not have 1, 2 or 3substituents which are selected, independently of one another, fromalkyl, halogen, CHF₂, CF₃, alkoxy, haloalkoxy, alkylthio, alkylsulfynyland alkylsulfonyl;

R¹ is a hydrogen atom;

R² is a phenyl or cycloalkyl group which may or may not have 1, 2 or 3substituents which are selected from alkyl, alkenyl, alkynyl, alkoxy,alkenyloxy, alkynyloxy, cycloalkyl, cyclo-alkenyl, cycloalkyloxy,cycloalkenyloxy, phenyl and halogen, where the aliphatic andcycloaliphatic radicals may be partially or fully halogenated and/or thecycloaliphatic radicals may be substituted by from 1 to 3 alkyl groupsand where the phenyl group may have from 1 to 5 halogen atoms and/orfrom 1 to 3 substituents which are selected, independently of oneanother, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio andhaloalkylthio, and where the amidic phenyl group may be condensed with asaturated 5-membered ring which may be substituted by one or more alkylgroups and/or may have a hetero atom selected from O and S, and theactive ingredient fenazaquin known as an acaricide.

These mixtures are described as being particularly effective againstBotrytis.

WO 97/40673 relates to fungicidal mixtures which inter alia compriseactive ingredients of the formulae IIa, IIb and/or IIc, in addition toother fungicidally active ingredients from the group of the oxime ethersand/or the carbamates.

Other fungicidal mixtures comprising active ingredients of the formulaeIIa to IIc are known from EP-A 797386, WO 97/06681, EP-B 425857, EP-B524496, EP-A 690792, WO 94/22308 and EP-B 645087.

It is an object of the present invention to provide other particularlyeffective mixtures for controlling harmful fungi and in particular forcertain indications.

Surprisingly we have found that this object is achieved by a mixturewhich comprises as active ingredients amide compounds of the formula Idefined at the outset and as further fungicidally active component afungicidally active ingredient from the group of the active morpholineand piperidine ingredients of the formulae IIa to IIc.

The mixtures according to the invention have synergistic action and aretherefore particularly suitable for controlling harmful fungi and inparticular powdery mildew fungi.

In the context of the present invention, halogen is fluorine, chlorine,bromine and iodine and is in particular fluorine, chlorine and bromine.

The term “alkyl” includes straight-chain and branched alkyl groups.These are preferably straight-chain or branched C₁-C₁₂-alkyl and inparticular C₁-C₆-alkyl groups. Examples of alkyl groups are alkyl suchas, in particular, methyl, ethyl, propyl, 1-methylethyl, butyl,1-methylpropyl, 2-methylpropyl, 1,1-di-methylethyl, n-pentyl,1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl,1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl,1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl,2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl,1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl.

Haloalkyl is an alkyl group as defined above which is partially or fullyhalogenated by one or more halogen atoms, in particular by fluorine andchlorine. Preferably, there are from 1 to 3 halogen atoms present, andthe difluoromethane [sic] or the trifluoromethyl group is particularlypreferred.

The above statements for the alkyl group and the haloalkyl group applyin a corresponding manner to the alkyl and haloalkyl groups in alkoxy,haloalkoxy, alkylthio, haloalkylthio, alkylsulfynyl and alkylsulfonyl.

The alkenyl group includes straight-chain and branched alkenyl groups.These are preferably straight-chain or branched C₃-C₁₂-alkenyl groupsand in particular C₃-C₆-alkenyl groups. Examples of alkenyl groups are2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl,2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl,2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl,1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl,3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl,1,1-dimethyl-3-butenyl, 1,1-dimethyl-3-butenyl [sic],1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl,1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl,1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, inparticular 2-propenyl, 2-butenyl, 3-methyl-2-butenyl and3-methyl-2-pentenyl.

The alkenyl group may be partially or fully halogenated by one or morehalogen atoms, in particular by fluorine or chlorine. The alkenyl grouppreferably has from 1 to 3 halogen atoms.

The alkynyl group includes straight-chain and branched alkynyl groups.These are preferably straight-chain and branched C₃-C₁₂-alkynyl groupsand in particular C₃-C₆-alkynyl groups. Examples of alkynyl groups are2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl,3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl,1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl,2-hexynyl, 3-hexynyl, 4-alkynyl [sic], 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl,1,2-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl,2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl.

The above statements for the alkenyl group and its halogen substituentsand for the alkynyl group apply in a corresponding manner to alkenyloxyand alkynyloxy.

The cycloalkyl group is preferably a C₃-C₆-cycloalkyl group, such ascyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. If the cycloalkylgroup is substituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicalsas substituents.

Cycloalkenyl is preferably a C₄-C₆-cycloalkenyl group, such ascyclobutenyl, cyclopentenyl or cyclohexenyl. If the cycloalkenyl groupis substituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

A cycloalkoxy group is preferably a C₅-C₆-cycloalkoxy group, such ascyclopentyloxy or cyclohexyloxy. If the cycloalkoxy group issubstituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

The cycloalkenyloxy group is preferably a C₅-C₆-cycloalkenyloxy group,such as cyclopentyloxy or cyclohexyloxy. If the cycloalkenyloxy group issubstituted, it preferably has from 1 to 3 C₁-C₄-alkyl radicals assubstituents.

Aryl is preferably phenyl.

If A is a phenyl group, this may have one, two or three of theabovementioned substituents in any position. These substituents arepreferably selected, independently of one another, from alkyl,difluoromethyl, trifluoromethyl and halogen, in particular chlorine,bromine and iodine. Particularly preferably, the phenyl group has asubstituent in the 2-position.

If A is a 5-membered heterocycle, it is in particular a furyl,thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazolyl orthiadiazolyl radical or the corresponding dihydro or tetrahydroderivatives thereof. Preference is given to a thiazolyl or pyrazolylradical.

If A is a 6-membered heterocycle, it is in particular a pyridyl radicalor a radical of the formula:

in which one of the radicals X and Y is O, S or NR¹², where R¹² is H oralkyl, and the other of the radicals X and Y is CH₂, S, SO, SO₂ or NR⁹.The dotted line means that a double bond may or may not be present.

The 6-membered aromatic heterocycle is particularly preferably a pyridylradical, in particular a 3-pyridyl radical, or a radical of the formula

in which X is CH₂, S, SO or SO₂.

The abovementioned heterocyclic radicals may or may not have 1, 2 or 3of the abovementioned substituents, where these substituents arepreferably selected, independently of one another, from alkyl, halogen,difluoromethyl or trifluoromethyl.

A is particularly preferably a radical of the formulae:

in which R³, R⁴, R⁶, R⁷, R⁸ and R⁹ independently of one another arehydrogen, alkyl, in particular methyl, halogen, in particular chlorine,CHF₂ or CF₃.

The radical R¹ in the formula I is preferably a hydrogen atom.

The radical R² in the formula I is preferably a phenyl radical. R²preferably has at least one substituent which is particularly preferablyin the 2-position. The substituent (or the substituents) is (are)preferably selected from the group consisting of alkyl, cycloalkyl,cycloalkenyl, halogen and phenyl.

The substituents of the radical R² may in turn be substituted again. Thealiphatic or cycloaliphatic substituents may be partially or fullyhalogenated, in particular fluorinated or chlorinated. They preferablyhave 1, 2 or 3 fluorine or chlorine atoms. If the substituent of theradical R² is a phenyl group, this phenyl group may preferably besubstituted by from 1 to 3 halogen atoms, in particular chlorine atoms,and/or by a radical which is preferably selected from alkyl and alkoxy.Particularly preferably, the phenyl group is substituted with a halogenatom in the p-position, i.e. the particularly preferred substituent ofthe radical R² is a p-halogen-substituted phenyl radical. The radical R²may also be condensed with a saturated 5-membered ring, where this ringfor its part may have from 1 to 3 alkyl substituents.

R² is in this case, for example, indanyl, thiaindanyl and oxaindanyl.Preference is given to indanyl and 2-oxaindanyl which are attached tothe nitrogen atom in particular via the 4-position.

According to a preferred embodiment, the composition according to theinvention comprises as amide compound a compound of the formula I inwhich A is as defined below:

phenyl, pyridyl, dihydropyranyl, dihydrooxathiynyl,dihydrooxathiynyloxide, dihydrooxathiynyldioxide, furyl, thiazolyl,pyrazolyl or oxazolyl, where these groups may have 1, 2 or 3substituents which are selected, independently of one another, fromalkyl, halogen, difluoromethyl and trifluoromethyl.

According to a further preferred embodiment, A is:

pyridin-3-yl, which may or may not be substituted in the 2-position byhalogen, methyl, difluoromethyl, trifluoromethyl, meth-oxy, methylthio,methylsulfynyl or methylsulfonyl;

phenyl, which may or may not be substituted in the 2-position by methyl,trifluoromethyl, chlorine, bromine or iodine;

2-methyl-5,6-dihydropyran-3-yl;

2-methyl-5,6-dihydro-1,4-oxathiyn-3-yl or the 4-oxide or 4,4-dioxidethereof;

2-methylfuran-3-yl, which may or may not be substituted in the 4- and/or5-position by methyl;

thiazol-5-yl, which may or may not be substituted in the 2- and/or4-position by methyl, chlorine, difluoromethyl or trifluoromethyl;

thiazol-4-yl, which may or may not be substituted in the 2- and/or5-position by methyl, chlorine, difluoromethyl or trifluoromethyl;

1-methylpyrazol-4-yl, which may or may not be substituted in the 3-and/or 5-position by methyl, chlorine, difluoromethyl ortrifluoromethyl; or

oxazol-5-yl, which may or may not be substituted in the 2- and/or4-position by methyl or chlorine.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formula Iin which R² is a phenyl group which may or may not be substituted by 1,2 or 3 of the abovementioned substituents.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formula Iin which R² is a phenyl group which has one of the followingsubstituents in the 2-position:

C₃-C₆-alkyl, C₅-C₆-cycloalkenyl, C₅-C₆-cycloalkyloxy, cycloalkenyloxy,where these groups may be substituted by 1, 2 or 3 C₁-C₄-alkyl groups,

phenyl, which is substituted by from 1 to 5 halogen atoms and/or from 1to 3 groups which are selected, independently of one another, fromC₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylthio and C₁-C₄-haloalkylthio,

indanyl or oxaindanyl which may or may not be substituted by 1, 2 or 3C₁-C₄-alkyl groups.

According to a further preferred embodiment, the compositions accordingto the invention comprise as amide compound a compound of the formulaIa,

in which

A is

X is methylene, sulfur, sulfynyl or sulfonyl (SO₂),

R³ is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine oriodine,

R⁴ is trifluoromethyl or chlorine,

R⁵ is hydrogen or methyl,

R⁶ is methyl, difluoromethyl, trifluoromethyl or chlorine,

R⁷ is hydrogen, methyl or chlorine,

R⁸ is methyl, difluoromethyl or trifluoromethyl,

R⁹ is hydrogen, methyl, difluoromethyl, trifluoromethyl or chlorine,

R¹⁰ is C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio or halogen.

According to a particularly preferred embodiment, the compositionscomprise as amide compound a compound of the formula Ib

in which

R⁴ is halogen and

R¹¹ is phenyl which is substituted by halogen.

Particularly preferred mixtures according to the invention comprise ascompounds of the formulae

Useful amide compounds of the formula I are mentioned in EP-A-545 099and 589 301 which are incorporated herein in their entirety byreference.

The preparation of the amide compounds of the formula I is known, forexample, from EP-A-545 099 or 589 301 or can be carried out by similarprocesses.

Also known are the morpholine and piperidine derivatives II (IIa: commonname: fenpropimorph, U.S. Pat. No. 4,202,894; IIb: common name:fenpropidin, U.S. Pat. No. 4,202,894; IIc: common name: tridemorph, DE-A11 64 152), their preparation and their action against harmful fungi.

To unfold synergistic activity, even a small amount of amide compound ofthe formula I is sufficient. Preference is given to employing amidecompound and morpholine or piperidine derivative in a weight ratio in arange of from 20:1 to 1:20, in particular 10:1 to 1:10.

Owing to the basic character of their nitrogen atoms, the compounds IIare capable of forming salts or adducts with inorganic or organic acidsor with metal ions.

Examples of inorganic acids are hydrohalic acids such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydriodic acid, sulfuricacid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid[sic] and alkanoic acids, such as acetic acid, trifluoroacetic acid,trichloroacetic acid and propionic acid, and also glycolic acid,thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid,cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids havingstraight-chain or branched alkyl radicals of 1 to 20 carbon atoms),arylsulfonic acids or aryldisulfonic acids (aromatic radicals, such asphenyl and naphthyl, which carry one or two sulfo groups),alkylphosphonic acids (phosphonic acids having straight-chain orbranched alkyl radicals of 1 to 20 carbon atoms), arylphosphonic acidsor aryldiphosphonic acids (aromatic radicals, such as phenyl andnaphthyl, which carry one or two phosphoric [sic] acid radicals), itbeing possible for the alkyl or aryl radicals to carry furthersubstituents, eg. p-toluenesulfonic acid, salicylic acid,p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid,etc.

Suitable metal ions are, in particular, the ions of the elements of thefirst to eighth sub-group, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and furthermore of the second main group,in particular calcium and magnesium, and of the third and fourth maingroup, in particular aluminum, tin and lead. The metals can exist in thevarious valencies which they can assume.

When preparing the mixtures, it is preferred to employ the pure activeingredients I and II, to which further active ingredients againstharmful fungi or other pests, such as insects, arachnids or nematodes,or else herbicidal or growth-regulating active ingredients orfertilizers can be admixed.

The mixtures of the compounds I and II, or the compounds I and II usedsimultaneously, jointly or separately, exhibit outstanding activityagainst a wide range of phytopathogenic fungi, in particular from theclasses of the Ascomycetes, Basidiomycetes, Phycomycetes andDeuteromycetes. Some of them act systemically and can therefore beemployed as foliar- and soil-acting fungicides.

They are especially important for controlling a large number of fungi ina variety of crop plants, such as cotton, vegetable species (eg.cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass,oats, bananas, coffee, maize, fruit species, rice, rye, soya, grapevine,wheat, ornamentals, sugar cane, and a variety of seeds.

They are particularly suitable for controlling the followingphytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals,Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,Podosphaera leucotricha in apples, Uncinula necator in grapevines,Puccinia species in cereals, Rhizoctonia species in cotton, rice andlawns, Ustilago species in cereals and sugar cane, Venturia inaequalis(scab) in apples, Helminthosporium species in cereals, Septoria nodorumin wheat, Botrytis cinera [sic] (gray mold) in strawberries, vegetables,ornamentals and grape-vines, Cercospora arachidicola in groundnuts,Pseudocercosporella herpotrichoides in wheat and barley, Pyriculariaoryzae in rice, Phytophthora infestans in potatoes and tomatoes,Plasmopara viticola in grapevines, Pseudoperonospora species in hops andcucumbers, Alternaria species in vegetables and fruit, Mycosphaerellaspecies in bananas and Fusarium and Verticillium species.

They can also be used for protecting material (e.g. protecting wood) forexample against Paecilomyces variotti.

The mixtures according to the invention may particularly prefer-ably beemployed for controlling powdery mildew fungi in crops of grapevines andcereals.

The compounds I and II can be applied simultaneously, either together orseparately, or in succession, the sequence, in the case of separateapplication, generally not having any effect on the result of thecontrol measures.

Depending on the kind of effect desired, the application rates of themixtures according to the invention are, in particular in agriculturalcrop areas, from 0.01 to 8 kg/ha, preferably 0.1 to 5 kg/ha, inparticular 0.2 to 3.0 kg/ha.

The application rates of the compounds I are from 0.01 to 2.5 kg/ha,preferably 0.05 to 2.5 kg/ha, in particular 0.1 to 1.0 kg/ha.

Correspondingly, in the case of the compounds II, the application ratesare from 0.01 to 10 kg/ha, preferably 0.05 to 5 kg/ha, in particular0.05 to 2.0 kg/ha.

For seed treatment, the application rates of the mixture are generallyfrom 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, inparticular 0.01 to 50 g/kg.

If phytopathogenic harmful fungi are to be controlled, the separate orjoint application of the compounds I and II or of the mixtures of thecompounds I and II is effected by spraying or dusting the seeds, theplants or the soils before or after sowing of the plants, or before orafter plant emergence.

The fungicidal synergistic mixtures according to the invention, or thecompounds I and II, can be formulated for example in the form ofready-to-spray solutions, powders and suspensions or in the form ofhighly concentrated aqueous, oily or other suspensions, dispersions,emulsions, oil dispersions, pastes, dusts, materials for broadcasting orgranules, and applied by spraying, atomizing, dusting, broadcasting orwatering. The use form depends on the intended purpose; in any case, itshould ensure as fine and uniform a distribution as possible of themixture according to the invention.

The formulations are prepared in a known manner, eg. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants, it being possible also to use other organicsolvents as auxiliary solvents if water is used as the diluent. Suitableauxiliaries for this purpose are essentially: solvents such as aromatics(eg. xylene), chlorinated aromatics (eg. chlorobenzenes), paraffins (eg.mineral oil fractions), alcohols (eg. methanol, butanol), ketones (eg.cyclohexanone), amines (eg. ethanolamine, dimethylformamide) and water;carriers such as ground natural minerals (eg. kaolins, clays, talc,chalk) and ground synthetic minerals (eg. finely divided silica,silicates); emulsifiers such as nonionic and anionic emulsifiers (eg.polyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates) and dispersants such as lignosulfite waste liquors andmethylcellulose.

Suitable surfactants are the alkali metal salts, alkaline earth metalsalts and ammonium salts of aromatic sulfonic acids, eg. ligno-,phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fattyacids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fattyalcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols,or of fatty alcohol glycol ethers, condensates of sulfonated naphthaleneand its derivatives with formaldehyde, condensates of naphthalene or ofthe naphthalenesulfonic acids with phenol and formaldehyde,polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl- ornonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycolethers, alkylaryl polyether alcohols, isotridecyl alcohol, fattyalcohol/ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers or polyoxypropylene [sic], lauryl alcoholpolyglycol ether acetate, sorbitol esters, lignosulfite waste liquors ormethylcellulose.

Powders, materials for broadcasting and dusts can be prepared by mixingor jointly grinding the compounds I or II, or the mixture of thecompounds I and II, with a solid carrier.

Granules (eg. coated granules, impregnated granules or homogeneousgranules) are usually prepared by binding the active ingredient, oractive ingredients, to a solid carrier.

Fillers or solid carriers are, for example, mineral earths, such assilica gel, silicas, silica gels [sic], silicates, talc, kaolin,limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth,calcium sulfate, magnesium sulfate, magnesium oxide, ground syntheticmaterials and fertilizers, such as ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders or other solid carriers.

The formulations generally comprise from 0.1 to 95% by weight,preferably 0.5 to 90% by weight, of one of the compounds I or II or ofthe mixture of the compounds I and II. The active ingredients areemployed in a purity of from 90% to 100%, preferably 95% to 100%(according to NMR or HPLC spectrum [sic]).

The compounds I and II, the mixtures, or the corresponding formulations,are applied by treating the harmful fungi, their habitat, or the plants,seeds, soils, areas, materials or spaces to be kept free from them witha fungicidally effective amount of the mixture, or of the compounds Iand II in the case of separate application.

Application can be effected before or after infection by the harmfulfungi.

Examples of such preparations comprising the active ingredients are:

I. A solution of 90 parts by weight of the active ingredients and 10parts by weight of N-methylpyrrolidone; this solution is suitable foruse in the form of microdrops;

II. A mixture of 20 parts by weight of the active ingredients, 80 partsby weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol ofethylene oxide to 1 mol of oleic acid N-monoethanolamide, 5 parts byweight of the calcium salt of dodecylbenzenesulfonic acid, 5 parts byweight of the adduct of 40 mol of ethylene oxide and 1 mol of castoroil; a dispersion is obtained by finely distributing the solution inwater;

III. An aqueous dispersion of 20 parts by weight of the activeingredients, 40 parts by weight of cyclohexanone, 30 parts by weight ofisobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxideand 1 mol of castor oil;

IV. An aqueous dispersion of 20 parts by weight of the activeingredients, 25 parts by weight of cyclohexanol, 65 parts by weight of amineral oil fraction of boiling point 210 to 280° C., and 10 parts byweight of the adduct of 40 mol of ethylene oxide and 1 mol of castoroil;

V. A mixture, ground in a hammer mill, of 80 parts by weight of theactive ingredients, 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 7 parts byweight of pulverulent silica gel; a spray mixture is obtained by finelydistributing the mixture in water;

VI. An intimate mixture of 3 parts by weight of the active ingredientsand 97 parts by weight of finely divided kaolin; this dust comprises 3%by weight of active ingredient;

VII. An intimate mixture of 30 parts by weight of the activeingredients, 92 parts by weight of pulverulent silica gel and 8 parts byweight of paraffin oil which had been sprayed onto the surface of thissilica gel; this formulation imparts good adhesion to the activeingredient;

VIII. A stable aqueous dispersion of 40 parts by weight of the activeingredients, 10 parts by weight of the sodium salt of a phenolsulfonicacid/urea/formaldehyde condensate, 2 parts by weight of silica gel and48 parts by weight of water; this dispersion may be diluted further;

IX. A stable oily dispersion of 20 parts by weight of the activeingredients, 2 parts by weight of the calcium salt ofdodecylbenzenesulfonic acid, 8 parts by weight of fatty alcoholpolyglycol ether, 20 parts by weight of the sodium salt of aphenolsulfonic acid/urea/formaldehyde condensate and 88 parts by weightof a paraffinic mineral oil.

USE EXAMPLE

The synergistic activity of the mixtures according to the invention canbe demonstrated by the following experiments:

The active ingredients, separately or together, are formulated as a 10%emulsion in a mixture of 63% by weight of cyclohexanone and 27% byweight of emulsifier, and diluted with water to the desiredconcentration.

Evaluation is carried out by determining the infected leaf areas inpercent. These percentages are converted into efficacies. The efficacy(W) is calculated as follows using Abbot's formula:

W=(1−α)·100/β

α corresponds to the fungal infection of the treated plants in % and

β corresponds to the fungal infection of the untreated (control) plantsin %

An efficacy of 0 means that the infection level of the treated plantscorresponds to that of the untreated control plants; an efficacy of 100means that the treated plants were not infected.

The expected efficacies of the mixtures of the active ingredients weredetermined using Colby's formula [R. S. Colby, Weeds 15, 20-22 (1967)]and compared with the observed efficacies.

 Colby formula: E=x+y−x·y/100

E expected efficacy, expressed in % of the untreated control, when usingthe mixture of the active ingredients A and B at the concentrations aand b

x efficacy, expressed in % of the untreated control, when using activeingredient A at a concentration of a

y efficacy, expressed in % of the untreated control, when using activeingredient B at a concentration of b

Use Example 1

Curative Activity Against Puccinia recondita on Wheat (Wheat Leaf Rust)

Leaves of potted wheat seedlings of the variety “Kanzler” were dustedwith spores of leaf rust (Puccinia recondita). Thereafter, the pots werekept for 24 hours in a chamber of high atmospheric humidity (90 to 95%)and 20 to 22° C. During this time, the spores germinated and thegerminal tubes penetrated into the leaf tissue. The next day, theinfected plants were sprayed to runoff point with an aqueous formulationof active ingredient prepared from a stock solution consisting of 10% ofactive ingredient, 63% of cyclohexanone and 27% of emulsifier. After thespray coating had dried on, the test plants were cultivated in agreenhouse at from 20 to 22° C. and from 65 to 70% of relativeatmospheric humidity for 7 days. Thereafter, the extent of rust fungusdevelopment on the leaves was determined.

The compounds of the formula I used were the following components:

The results are shown in Tables 1 and 2 below.

TABLE 1 Concentration of active ingredient Active ingredient in thespray liquor Efficacy in % of Ex. (content in ppm) in ppm the untreatedcontrol IC Control untreated (100% infection)  0 2C Compound I.1 63  016  0 3C Compound I.2 16  0 4C Compound IIa 16 20 5C Compound IIb 16 206C Compound IIc 63  0

TABLE 2 Mixtures according to the invention Observed Calculated Ex.(content in ppm) efficacy efficacy*)  7 16 ppm I.1 + 50 20 16 ppm IIa  816 ppm I.1 + 40 20 16 ppm IIb  9 63 ppm I.1 + 25  0 63 ppm IIc 10 16 ppmI.2 + 50 20 16 ppm II.a 11 16 ppm I.2 + 45 20 16 ppm II.b *)calculatedusing Colby's formula

The test results show that the observed efficacy in all mixing ratios ishigher than the efficacy which had been calculated beforehand usingColby's formula

Use Example 2

Activity Against Powdery Mildew of Wheat

Leaves of potted wheat seedlings of the variety “Kanzler” were sprayedto runoff point with an aqueous formulation of active ingredientprepared from a stock solution consisting of 10% of active ingredient,63% of cyclohexanone and 27% of emulsifier and 24 hours after the spraycoating had dried on, the leaves were dusted with spores of powderymildew of wheat (Erysiphe graminis forma specialis tritici). The testplants were subsequently kept in a greenhouse at 20 to 24° C. and 60 to90% relative atmospheric humidity. After 7 days, the extent of themildew development was determined visually in % infection of the totalleaf area.

The test results are shown in Tables 3 and 4 below.

TABLE 3 Concentration of active ingredient Active ingredient in thespray liquor Efficacy in % of Ex. (content in ppm) in ppm the untreatedcontrol 12C Control untreated  0  0 (100% infection) 13C Compound I.1 16 0  4  0 14C Compound I.2  4  0  1  0 15C Compound IIa  4 20  1  0 16CCompound IIb  4 30  1  0 17C Compound IIc 16 20  4  0

TABLE 4 Mixtures according to the invention Observed Calculated Ex.(content in ppm) efficacy efficacy*) 18 4 ppm I.1 + 40 20 4 ppm IIa 19 4ppm I.1 + 45 30 4 ppm II.b 20 16 ppm I.1 + 35 20 16 ppm IIc 21 4 ppmI.2 + 70 20 4 ppm IIa 22 1 ppm I.2 + 20  0 1 ppm IIa 23 1 ppm I.2 + 25 0 1 ppm IIc *)calculated using Colby's formula

The test results show that for all mixing ratios the observed efficacyis higher than the efficacy which had been calculated beforehand usingColby's formula

We claim:
 1. A synergistically effective fungicidal mixture comprisingas active components a) an amide compound of the formula Ia

 in which A is

R⁴ is chlorine; R¹⁰ is halogen; and b) a morphine or piperdinederivative II selected from the group of compounds IIa, IIb and IIc

wherein the mixture of a) and b) possesses synergistic antifungalactivity.
 2. A synergistically effective fungicidal mixture as claimedin claim 1, which comprises as amide compound a compound of the formulaebelow:


3. A fungicidal mixture as claimed in claim 1, which is comprises twoparts, one part comprising the amide compound in a solid or liquidcarrier and the other part comprising one or more compounds of theformulae IIa to IIc in a solid or liquid carrier.
 4. A method forcontrolling phytopathogenic fungi, which comprises treating the fungi,their habitat, or the materials, plants, seeds, soils, areas or spacesto be protected against fungal attack with a fungicidal mixture asclaimed in claim 1, where the application of the active ingredientsamide compound I and one or more compounds of the formulae IIa to IIcmay be carried out together or in succession.